Process for obtaining hydrogenation gas for hydrogenating carbon and hydrocarbons from gases containing methane and hydrogen



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Jan. 15, 1929. 1,699,177

HYDROGENATING Anson Ann HYnRocARoNs non GASES CONTAINING HETHANE Arm lmmoau F. BERGIUS PROCESS FOR OBTAINING HYDROGENATION GAS FOR Filed Nov. 30, 1925 /n ven tok:

01W. ns A Q Patented Jan. 1.5, A192.9. A UNITED STATES PATENT OFFICE.

, rnrnnmen BEnG'IUs, OFHHEIDELBERG, GERMANY.

PROCESS FOB OBTAINIIlG HYDROGENATION GAS FOR HYDROGENATING `CARBN AND HYDROCARBQNS FROM GASES CONTAINING METHANE HYDBOGEN.

l Application filed November 30, 1925, Serial No..72,414, and in Germany December 18, 1924.

In the'hydrogenation of carbon and hydrocarbons under high pressure, waste gases are formed which consist vchiefly of methane (CIL) and vits homologues with hydrogen and small quant-ities of alien gases, chief among which are nitrogen, carbon monoxide (CO) and carbonic acid (CO2) The relatively considerable quantity of hydrogen contained in these waste gases .can only be used for heating purposes, unless one succeeds in transforming the waste gases into ahydrogenation gas sufficiently rich, cally sound means. It is indeed well known that the uncondensable hydrocarbons which `the i waste gases contain in considerable quantity, can be converted into hydrogen, either by breaking them up merely by the application of temperatures of 1000o and above or by converting them in the presence of steam of water. Both processes are however practically inadequate in themselves for the purpose of regenerating the waste gases, because with the mere analytic reaction', the hydrogen gained is not sutlicient for the purpose of using the gas once more as hydrogenation gas and also because, at the same timey as hydrogen, carbon monoxide is produced in such quantities that the hydrogen'ating" process and the circulation of thegas cannot be successfully kept up.

The resent invention overcomes this difficulty by subjecting the waste gases, which consist principally of methane and hydrogen, to treatment with steam at. various temperatures namely, toa first treatment at a high temperature and then to another treatment at a lower temperature, the first treatment leading to the conversion, referred to above, ofV the methane into hydrogen and carbon monoxide, while the last treatment converts the carbn monoxide, in a manner likewise well known in itself, into hydrogen and carbonio acid, this-last body, in contrast to carbon monoxide, being easily removable by well known processes. The removal of the carbonioV acidis effected for the purposein view before the gas is utilized as hydrogena-` tion gas but it can also take place at any time in the course of the process, which is a continuous cyclic one,- after every new util'zation of the gas for hydrogenating purpo The .accumulation of alien gases, and espeeially nitrogen, in the gas mixture in the case of the continuous cyclic process can be avoided by removing from the circulation a sufin hydrogen by eeonomi-' iciently large portion of the gas. The possibility of doing this without jeopardizing the continuous use of the regenerated gas in a recurrent circle, depends on the extraordinary "increase of hydrogen, through the treatment of the gases with steam, this leading to the formation ofhydrogen at each of the two stages of the operation.

In given circumstances al plant for the hydrogenation of carbon and hydrocarbons may work in close connection with a coke making plant, for instance, the latter supplying for lts part gases containing methane and hydrogen. lIn this case the process described here for obtaining hydrogenationigas from gases containing methane and hydrogen can also 'be applied to the gases of the coke works and these gases could be used instead of t-he con verted gases of the hydrogenation plant, for the work of that plant. A plant for carrying out theprocess described above is diagrammatically shown in its chief features in the drawing appended hereto.

1 'shows the reaction chamber of a. hydrogenation plant. 2 is the condenser for the condensible bodies, 3 is the trap `,or receiver in which, the liquid condensed products are vcatalyzing apparatus, into which the gaf-es are brought for the purpose of the reaction withlsteam at the lower temperature stage, for the purpose of converting the `carbon monoxide, formed during th f reaction .at the high temperature, into 4car ionic acid.

As the carrying out of the hydrogenation process 'does not demand a gas free from carbon monoxide, the p-resence of` carbon monoxide in the hydrogenating Vg'asbeing rather a disadvantage only in so'far as it reduces the pressure which the active hydrogen would exert if it were alone present, vit is, therefore not necessary to carry out to the full the process of converting4 the carbonv monoxide into carbonic acid which can be easily removedpby washing or similar means, but one can leave a certain percentage of fas carbon monoxide in the gas. The process thereby gains considerably from the economic point of view. 9 showsI a" steam .admission pipe for the catalyzing'apparatus. The reaction in the catalyzing apparatus takes place in the well known mannerl with the employment of a suitable catalytic agent, iron oxide, for instance. 'Instead of steam, water can also be introduced into the hot gases, the evaporation then taking place through the hea-t contained in these gases subject to the conditions that. one should be careful not to allow the temperature to fall below the temperature which must exist'in the catalyzing apparatus in order to permit the reaction to take place.l

The working temperature at the high temperature stage is approximately 1100" and at the low temperature it is from 300 to 500o approximately. 10 shows a cooling apparatus for the regenerated gas, 11 shows a preliminary compression pump and 12 a wash tower for the removal of the carbonic acid. By means of compressor 13, the ready hydrogenation gas is brought to the working pressure, in order to introduce it once more into the reaction tank l. 14 shows the pipe lead for the hydrogenation gas. 15 a pipe for taking away the hydrogenation products which are not in gaseous form; 16 is a lead intended for the removal of the excess of gas given out.

IVhat I claim is:

1. Process which comprises subjecting waste hydrogenation gas such as that obtained in the hydrogenation. of coal to steam treatment in two successive stages at ditferenttemperatures, the treating temperaturein the iirst stage being the higher one and being chosen sufiiciently high to decompose methane in the absence of a catalyzer and to give ris'e to the formation of carbon monoxide and hydrogen and the lower temperature steam treatment being carried through in the presence of a catalyzer adapted to enhance the reaction between carbon monoxide and steam, 2. In processes of liydrogenating carbon containing material by treating itwitli hydrogen-containing gas under pressure, subjecting the resulting gases to a condensing treatment, and separating the condensate from the uncondensed waste gases, treating the uncondensed waste gases with added steam at a temperature suiicient to bring about a reaction with formation of hydrogen and carbon monoxide, bringing the carbon monoxide constituent of the resulting gases into reaction with steam at a lower temperature and in the presence of a catalyzer adapted to enhance using the so modified this reaction', removing carbon dioxide from the gases after the last named treatment and gas iii the hydrogenatioii reaction. y v

3. In processes for the hydrogenation of carbon-containing material involving treating the material under pressure with a gas consisting essentially of hydrogen, subjecting .the resulting waste gases to a condensing operation and separating condensate from the uncondensed waste gases consisting for the most part of hydrogen and methane-type hydrocarbons with carbon monoxide, carbon dioxide, and nitrogen, the steps which consist in reacting the uiicondensed waste gases with steam in the absence of a promoter of reaction and at a temperature of about 1100o C. to the decomposition of the methane-type hydrocarbons and steam to hydrogen and. carbon monoxide, adding steam tothe resulting gas mixture, reacting the steam with the carbon.,

monoxide content of the said resulting gas mixture in the presence of a'suitable catalyst and at a temperatureof from about 300 to about 500o tothe production of hydrogen andthe conversion ofqcarbon monoxide to carbon dioxide, thereafter removing the carbon dioxide content of the gas mixture and rev turning the residual operation.

4. In processes for the hydrogenation of carbon-containing material involving treating the material under pressure with a gas consisting essentially of hydrogen, subjecting the resulting waste gases to a condensing operation and separating condensate from lthe ,uncondensed waste gases consisting for the most part of hydrogen and methane-type hydrocarbons with carbon monoxide, carbon dioxide, and nitrogen, the steps which consist in reacting the uncondensed waste gases with steam in the absence of a promoter ofreaction and at a temperature of about 1100o C. to the gas tothe hydrogenation decomposition of the inetliane-type hydro-.

carbons and steam to hydrogen and carbon monoxide, contacting theresulting gas mix- .ture with water to the simultaneous addition of water vapor and reduction in the temperature of the gas mixture, passing the gas mixture containing water vapor at from about 300o to about 500 C. .over a suitable catalyst,

to the conversion of its carbon monoxide and water vapor contents to hydrogen and carbon dioxide, removing the carbon dioxide `content;

of the gas mixture, and returning the residual gas to the hydrogenation operation.

Iii testimony whereof, I affix my signature.

DR. FRIEDRICH BERGIUS. 

